The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl Ylide
Aim. To study the use of chloromethyl trimethylsilylmethyl sulfide as a precursor of thiocarbonyl ylide in [3+2] cycloaddition reaction to a number of α,β-unsaturated compounds and to establish the regularities of the reaction course. To develop an effective method for the synthesis of new dihydro-...
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| Format: | Article |
| Language: | English |
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National University of Pharmacy (Kharkiv, Ukraine)
2023-06-01
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| Series: | Журнал органічної та фармацевтичної хімії |
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| Online Access: | https://ophcj.nuph.edu.ua/article/view/283517 |
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| author | Tymofii V. Rudenko Vadim M. Timoshenko |
| author_facet | Tymofii V. Rudenko Vadim M. Timoshenko |
| author_sort | Tymofii V. Rudenko |
| collection | DOAJ |
| description | Aim. To study the use of chloromethyl trimethylsilylmethyl sulfide as a precursor of thiocarbonyl ylide in [3+2] cycloaddition reaction to a number of α,β-unsaturated compounds and to establish the regularities of the reaction course. To develop an effective method for the synthesis of new dihydro- and tetrahydrothiophene derivatives which are convenient for further modification.
Results and discussion. The synthetic approach to tetrahydrothiophenes with substituents in positions 3 and 4 was extended by the [3+2] cycloaddition reaction of thiocarbonyl ylide with a number of compounds containing an activated multiple bond. The stereoselectivity and limitations of this reaction were determined. Further functionalization of the obtained compounds was carried out.
Experimental part. Thiocarbonyl ylide was obtained by fluoride ion-promoted 1,3-desilylation of the known chloromethyl trimethylsilylmethyl sulfide. The synthesis of the target compounds involved the [3+2] cycloaddition of such an ylide to a series of compounds with an activated multiple bond. The stereochemistry of the target compounds was determined by 1H NOESY experiments. Synthetic derivatives of thiolancarboxylic acids, in particular aldehydes, alcohols, amines, amidines, were obtained by functionalization of the [3+2] adducts.
Conclusions. The synthetic approach to functionalized tetrahydrothiophenes by the [3+2] cycloaddition reaction of thiocarbonyl ylide with a number of compounds containing an activated multiple bond has expanded the limits of application of this reaction and allows obtaining the target compounds in multigram quantities. A high stereoselectivity of this reaction was observed. The reaction products are convenient synthetic precursors to the various classes of organic compounds. |
| first_indexed | 2024-03-12T12:15:19Z |
| format | Article |
| id | doaj.art-04141c109ad24b65b41692b13a48336a |
| institution | Directory Open Access Journal |
| issn | 2308-8303 2518-1548 |
| language | English |
| last_indexed | 2024-03-12T12:15:19Z |
| publishDate | 2023-06-01 |
| publisher | National University of Pharmacy (Kharkiv, Ukraine) |
| record_format | Article |
| series | Журнал органічної та фармацевтичної хімії |
| spelling | doaj.art-04141c109ad24b65b41692b13a48336a2023-08-30T14:10:07ZengNational University of Pharmacy (Kharkiv, Ukraine)Журнал органічної та фармацевтичної хімії2308-83032518-15482023-06-01212536310.24959/ophcj.23.283517The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl YlideTymofii V. Rudenko0Vadim M. Timoshenko1https://orcid.org/0000-0002-4879-604XInstitute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine; Enamine Ltd., UkraineInstitute of Organic Chemistry of the National Academy of Sciences of Ukraine, UkraineAim. To study the use of chloromethyl trimethylsilylmethyl sulfide as a precursor of thiocarbonyl ylide in [3+2] cycloaddition reaction to a number of α,β-unsaturated compounds and to establish the regularities of the reaction course. To develop an effective method for the synthesis of new dihydro- and tetrahydrothiophene derivatives which are convenient for further modification. Results and discussion. The synthetic approach to tetrahydrothiophenes with substituents in positions 3 and 4 was extended by the [3+2] cycloaddition reaction of thiocarbonyl ylide with a number of compounds containing an activated multiple bond. The stereoselectivity and limitations of this reaction were determined. Further functionalization of the obtained compounds was carried out. Experimental part. Thiocarbonyl ylide was obtained by fluoride ion-promoted 1,3-desilylation of the known chloromethyl trimethylsilylmethyl sulfide. The synthesis of the target compounds involved the [3+2] cycloaddition of such an ylide to a series of compounds with an activated multiple bond. The stereochemistry of the target compounds was determined by 1H NOESY experiments. Synthetic derivatives of thiolancarboxylic acids, in particular aldehydes, alcohols, amines, amidines, were obtained by functionalization of the [3+2] adducts. Conclusions. The synthetic approach to functionalized tetrahydrothiophenes by the [3+2] cycloaddition reaction of thiocarbonyl ylide with a number of compounds containing an activated multiple bond has expanded the limits of application of this reaction and allows obtaining the target compounds in multigram quantities. A high stereoselectivity of this reaction was observed. The reaction products are convenient synthetic precursors to the various classes of organic compounds.https://ophcj.nuph.edu.ua/article/view/283517cycloadditionthiocarbonyl ylidedipolarophiledihydrothiophenetetrahydrothiophene |
| spellingShingle | Tymofii V. Rudenko Vadim M. Timoshenko The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl Ylide Журнал органічної та фармацевтичної хімії cycloaddition thiocarbonyl ylide dipolarophile dihydrothiophene tetrahydrothiophene |
| title | The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl Ylide |
| title_full | The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl Ylide |
| title_fullStr | The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl Ylide |
| title_full_unstemmed | The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl Ylide |
| title_short | The Synthesis of the Hydrogenated Thiophenes by [3+2] Cycloaddition Reaction of Thiocarbonyl Ylide |
| title_sort | synthesis of the hydrogenated thiophenes by 3 2 cycloaddition reaction of thiocarbonyl ylide |
| topic | cycloaddition thiocarbonyl ylide dipolarophile dihydrothiophene tetrahydrothiophene |
| url | https://ophcj.nuph.edu.ua/article/view/283517 |
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